JP3460005B2 - Hydrogenated polymer - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrogenated polymer obtained by hydrogenating a conjugated diene polymer obtained by anionic polymerization, and relates to a hydrogenated polymer having markedly improved weather resistance.

[0002]

2. Description of the Related Art Hydrogenated polymers obtained by hydrogenating a conjugated diene polymer obtained by anionic polymerization are N
Known are hydrogenated polymers obtained by hydrogenation using a metal catalyst such as i, Co, Pd and Pt, and hydrogenated polymers obtained by using a Ti compound described in JP-A-59-133203 as a catalyst. Has been. Among these hydrogenated polymers, hydrogenated polymers in which 90% or more of double bonds based on conjugated dienes are hydrogenated are known, but when one molecular chain of the hydrogenated polymer is taken out, , The method for confirming whether or not the polymer is 100% completely hydrogenated polymer, and the analysis method and the confirmation method for the hydrogenated polymer consisting only of 100% completely hydrogenated polymer still remain. The current situation is that it has not been developed.

[0003]

The hydrogenated polymers obtained so far have a markedly improved thermal stability due to the reduction of double bonds, but have a small amount of weather resistance, ozone resistance and the like. Since the double bond is used, it is far inferior to polyethylene which has no double bond at all, and its improvement has been demanded. An object of the present invention is to improve the weather resistance of such a hydrogenated polymer.

[0004]

Means for Solving the Problems As a result of intensive studies conducted by the present inventors to improve the above weather resistance, the hydrogenated conjugated diene polymer has an average hydrogenation rate of 90% or more, And, when the hydrogenated polymer is decomposed by ozonolysis, a component having the same molecular weight as the component having the highest molecular weight in the hydrogenated polymer before ozone decomposition, that is, a high molecular weight component which does not undergo ozonolysis is It has been found that weatherability is significantly improved in hydrogenated polymers present in specific amounts.

That is, the present invention is a conjugated diene polymer obtained by anionic polymerization, a copolymer of a conjugated diene having a vinyl aromatic hydrocarbon content (S) of 70% by weight or less, and a vinyl aromatic hydrocarbon, or a copolymer thereof. Heavy consisting of a mixture of
The combined solution, hydrogen gas, and hydrogenation catalyst are continuously equipped with a stirrer
To the hydrogenation reaction tank and continuously take out the reaction product.
A hydrogenated polymer obtained by hydrogenating an aliphatic double bond mainly based on a conjugated diene in a polymer obtained by a continuous hydrogenation method , wherein the hydrogenated polymer has a normalized GPC curve (A). The length of a vertical line L drawn from the apex of the peak of the maximum molecular weight component of the peak to the base line is L1, and the normalized GPC of the decomposition product obtained by ozone decomposition of the hydrogenated polymer
When the curve (B) is superposed on the GPC curve (A) at the same elution time and the distance on the perpendicular L between the intersection point where the GPC curve (B) intersects the perpendicular L and the baseline is L2, Average hydrogenation rate (H) of double bond based on conjugated diene, characterized in that L2 / L1 is 0.02 or more
(%) Is a value that satisfies the following general formula (1), and GP
The styrene-equivalent weight average molecular weight obtained in C is 30,0.
0 to 1,000,000 hydrogenated polymer and its water
Involved in a method for producing an addition polymer .

[0006]

[Formula 2] Here, GPC is a gel permeation chromatograph, which is a kind of molecular weight measurement method for polymer substances, and a GPC curve is a molecular weight distribution curve measured by GPC.

Explaining the present invention in detail, the ozone decomposition method used in the present invention can be carried out by the method of Tanaka et al. For example Y.Tanaka, H.Sato, Y.Nakafutam
i, Y. Kashiwazaki, Macromolecules, 16 (12) , 1925 (198
It is the method described in 3). When the molecular weight distribution of the decomposed polymer obtained by the above ozone decomposition method was measured using GPC, which was used to measure the molecular weight distribution of the polymer after hydrogenation, there was no change in the GPC curve and the molecular weight distributions were completely in agreement. In some cases, it can be said that the hydrogenated polymer did not undergo ozonolysis. However, this means that the hydrogenated polymer is 1
It does not indicate that it is completely hydrogenated to 100%. In the present invention, it is necessary that the amount of the hydrogenated polymer component that has not undergone ozonolysis be present in a specific amount or more,
The quantitative method is defined below.

The normalized GPC curve (A) of the conjugated diene-based polymer before hydrogenation was made to correspond to the normalized GPC curve (B) of the decomposition product obtained by ozone decomposition of the hydrogenated polymer, and the elution times were matched. When superposed on the GPC curve (A), the length of the perpendicular line L drawn from the apex of the peak of the maximum molecular weight component among the peaks in the GPC curve (A) to the baseline is L1, and the GPC curve (B) is the perpendicular line. L2 / L1 is obtained by setting the distance on the perpendicular line L between the intersection and the base line intersecting L and L2, and the amount of this L2 / L1 is defined as the amount of hydrogenated polymer component that has not been subjected to ozone decomposition.

The average hydrogenation rate (H) (%) of the present invention is a value satisfying the general formula (1), and L2 / L1 is 0.01.
As the hydrogenated polymer described above, a Ti compound described in JP-A-59-133203 or JP-A-60-79005 is used as a hydrogenation catalyst, and the hydrogenation catalyst, hydrogen gas, unhydrogenated polymer is used. Can be obtained by a continuous hydrogenation method in which the product is continuously supplied to a reaction vessel equipped with a stirrer and the product is continuously extracted. In this continuous hydrogenation method, because there are polymers with different hydrogenation rates in the hydrogenation reaction tank, not only the extracted hydrogenated polymer also becomes a polymer having a hydrogenation rate distribution,
Compared with the batch hydrogenation method, the hydrogenation rate tends to be lower, but a hydrogenated polymer with a high hydrogenation rate can be stably obtained by holding it in the pipe for transferring from the hydrogenation reaction tank to the degassing tank for 3 minutes or more. be able to.

Generally, a hydrogenation reaction carried out using a metal catalyst such as Ni, Co, Pd, Pt, or Ti is carried out by charging a hydrogenation reaction tank with a conjugated diene polymer and a hydrogenation catalyst before hydrogenation. A batch type hydrogenation reaction in which gas is introduced at a predetermined pressure is used, but in this reaction method, the average hydrogenation rate approaches 100% when the hydrogenation reaction is repeated or the hydrogenation reaction time is lengthened. However, L2 / L1 of the hydrogenated polymer obtained by such a batch type hydrogenation reaction is 0 to 0.0
It is a low value of about 1. That is, in the batch type hydrogenation reaction, most of the polymer chains are broken by ozonolysis, so that L2 / L1 becomes less than 0.02, and the hydrogenated polymer is stretched in a weather resistance test by a fade meter. Strength decreases in a short time. On the other hand, the average hydrogenation rate (H) (%) of the invention of the present application is a value satisfying the general formula (1), and L2 / L1 is 0.02 or more. The decrease of is small. This is because there is a small amount of polymer molecular chains that are not decomposed at all by ozonolysis, and since there are many polymer parts even after ozonolysis, the decrease in tensile strength due to the weather resistance test is lessened. It is considered to be something.

Average hydrogenation rate (H) of the hydrogenated polymer of the present invention
(%) Is a value that satisfies the general formula (1). If the average hydrogenation rate is less than 90%, the weather resistance and thermal stability of the hydrogenated polymer will deteriorate, which is not preferable. Further, if the hydrogenation rate is higher than the range of the general formula (1), the productivity is remarkably reduced, or the polymer molecular chain is broken by the hydrogenation reaction, so that the mechanical properties of the hydrogenated polymer are improved. descend.

The molecular weight of the hydrogenated polymer of the present invention is 30,000 to 1,000,000 as styrene-equivalent weight average molecular weight (Mw) determined by GPC, and preferably 40,000 to 500,000. . Mw is 30,
If it is less than 000, the mechanical strength of the hydrogenated polymer is not sufficient,
When it exceeds 1,000,000, it becomes difficult to handle the polymer.

The hydrogenated polymer of the present invention is a conjugated diene polymer obtained by anionic polymerization, a copolymer of a conjugated diene having a vinyl aromatic hydrocarbon content of 70% by weight or less and a vinyl aromatic hydrocarbon, or a copolymer thereof. Is a hydrogenated polymer obtained by hydrogenating an aliphatic double bond mainly based on a conjugated diene in a polymer composed of a mixture of
1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene,
1,3-cyclohexadiene and the like can be used, but generally 1,3-butadiene, 2-methyl-1,3
-Butadiene (isoprene) is used. Further, as the vinyl aromatic hydrocarbon, use styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, α-methylstyrene, vinylnaphthalene, vinylanthracene, 1,1-diphenylethylene, or the like. You can Generally, styrene, α-methylstyrene and 1,1-diphenylethylene are used. These conjugated dienes and vinyl aromatic hydrocarbons may be used alone or in combination of two or more.

Polymers obtained by anionic polymerization using these conjugated dienes and vinyl aromatic hydrocarbons include the following polymers depending on the bonding form of the monomers. That is, the composition of the conjugated diene homopolymer, the random copolymer of a conjugated diene and a vinyl aromatic hydrocarbon, the block copolymer of a conjugated diene and a vinyl aromatic hydrocarbon, and the random portion of the conjugated diene and a vinyl aromatic hydrocarbon are So-called taper structure polymers that change continuously, block polymers with different microstructures (vinyl, cis, trans) based on conjugated dienes, taper polymers that change microstructure continuously, vinyl aromatic hydrocarbon content Block copolymer consisting of different random copolymers, bifunctional coupling polymer obtained by coupling agent or branching agent, or thermal branching, radial polymer, branched polymer, polyfunctional polymerization initiator Chain or branched polymer,
Polymers having a broad molecular weight distribution and composition distribution due to multistage addition of an initiator or forced deactivation, and the like, but also polymers obtained by combining the above polymers and copolymers are included. Hydrogenation weight obtained by hydrogenating a block copolymer having at least two blocks mainly containing vinyl aromatic hydrocarbons and at least one block mainly containing conjugated dienes among these polymers Coalescence is particularly useful as a base polymer for elastomeric compositions.

A conjugated diene polymer obtained by these anionic polymerizations, a copolymer of a conjugated diene having a vinyl aromatic hydrocarbon content of 70% by weight or less and a vinyl aromatic hydrocarbon, or a mixture thereof. Can be obtained by a known anionic polymerization method. Solvents that can be used in the polymerization reaction include linear, branched and cyclic hydrocarbon solvents such as butane, butene, pentane, hexane, octane, cyclohexane, benzene, toluene,
Examples include xylene, decalin, tetralin, linear and cyclic ethers such as diethyl ether and hetrahydrofuran. Hexane and cyclohexane are preferred. The initiator used for the polymerization is n-butyllithium,
sec-Butyllithium, other alkali metal initiators, and polyfunctional initiators can also be used.

The preferred polymerization temperature is -78 ° C to 150 ° C.
However, it is preferably 10 ° C to 120 ° C in order to control the productivity and the microstructure of the polymer.
A polar compound may be added and polymerized in order to control the microstructure of the polymer, and an ether compound or a tertiary amino compound is used as the polar compound, and examples thereof include tetrahydrofuran, diglyme, tetramethylethylenediamine, and bis-oxolanyl. Examples include propane.
It is also possible to couple the active living polymer into a linear or branched polymer. Coupling agents include halogen compounds, epoxy compounds, carbonyl compounds and the like, and examples thereof include silicon tetrachloride, carbon tetrachloride, ethylene dibromide, diglycidyl compounds, ethyl acetate and the like. It is also possible to add compounds with active hydrogens to deactivate some active living polymers during the polymerization.

The polymer of which the polymerization is completed can be used as it is, or the living polymer can be deactivated with alcohol, water or hydrogen gas to be subjected to the hydrogenation reaction, or the polymer can be taken out from the solution and then the hydrogenation reaction can be carried out. You can also use it. The alcohol used is preferably an alcohol having 1 to 12 carbon atoms such as methanol, ethanol, propanol, and isopropanol.

The hydrogenated polymer of the present invention uses a Ti compound as a hydrogenation catalyst, and continuously supplies the hydrogenation catalyst, hydrogen gas and unhydrogenated polymer to a reaction vessel equipped with a stirrer. Can be obtained by a continuous hydrogenation method of continuously extracting. It is desirable that the polymer obtained by the batch polymerization is once stored in a buffer tank and then subjected to the continuous hydrogenation reaction, and the polymer obtained by the continuous polymerization reaction is continuously subjected to the continuous hydrogenation reaction as it is.

For some hydrogenation catalysts whose hydrogenation activity changes during storage, it is necessary to add a catalyst having a high activity to the reaction tank. Therefore, a catalyst exhibiting a high activity for a short period of time must be continuously added to the reaction tank in a state of exhibiting an optimum activity while continuously adjusting the catalyst, while a catalyst exhibiting a high activity for a long period of time requires the catalyst to be added beforehand. After adjustment, it can be continuously added to the reaction tank in small amounts within a time period in which high activity is maintained. A preferred hydrogenation catalyst is a Ti compound represented by the following general formula 2.

[0020]

## STR2 ## Cp ₂ MRR '··· ₍₂₎ wherein, Cp is a an optionally substituted cyclopentadienyl group in the alkyl group, M is titanium, zirconium, a metal selected from hafnium, R , R ′ represents a group selected from halogen, alkyl having 1 to 12 carbons and aryl, and R and R ′ may be the same or different. ]

Specific Ti compounds include bis (η ⁵
-Cyclopentadienyl) titanium dimethyl, bis (η ⁵ -cyclopentadienyl) titanium diethyl,
Bis (η ⁵ -cyclopentadienyl) titanium dipropyl, bis (η ⁵ -cyclopentadienyl) titanium di-n-butyl, bis (η ⁵ -cyclopentadienyl)
Titanium di-sec-butyl, bis (η ⁵ -cyclopentadienyl) titanium dihexyl, bis (η ⁵ -cyclopentadienyl) titanium dioctyl, bis (η
⁵ -cyclopentadienyl) titanium dimethoxide,
Bis (η ⁵ -cyclopentadienyl) titanium diethoxide, bis (η ⁵ -cyclopentadienyl) titanium dipropoxide, bis (η ⁵ -cyclopentadienyl) titanium dibutoxide, bis (η ⁵ -cyclo Pentadienyl) titanium diphenyl, bis (η ⁵ -cyclopentadienyl) titanium di-m-tolyl, bis (η ⁵ -cyclopentadienyl) titanium di-p-tolyl, bis (η ⁵ -cyclopentadienyl) ) Titanium di-m, p-xylyl, bis (η ⁵ -cyclopentadienyl) titanium di-4-ethylphenyl, bis (η ⁵
- cyclopentadienyl) titanium di-4-hexylphenyl, bis (eta ⁵ - cyclopentadienyl) titanium diphenoxide, bis (eta ⁵ - cyclopentadienyl) titanium difluoride, bis (eta ⁵ - cyclopenta Dienyl) titanium dibromide, bis (η ⁵ −
Cyclopentadienyl) titanium dichloride, bis (η ⁵ -cyclopentadienyl) titanium dibromide, bis (η ⁵ -cyclopentadienyl) titanium diiodide, bis (η ⁵ -cyclopentadienyl) titanium chloride methyl , Bis (η ⁵ -cyclopentadienyl) titanium chloride ethoxide, bis (η ⁵ -cyclopentadienyl) titanium chloride phenoxide, bis (η ⁵ -cyclopentadienyl) titanium dibenzyl and the like. These can be used alone or in combination. Among these, preferred compounds are bis (η ⁵ -cyclopentadienyl) titanium di-m-tolyl, bis (η ⁵ -cyclopentadienyl) titanium di-p-tolyl and bis (η ⁵
-Cyclopentadienyl) titanium dichloride.

Examples of compounds that reduce these Ti compounds include metal compounds and organometallic compounds. Examples of the organometallic compound include organolithium compounds, organosodium compounds, organopotassium compounds, organozinc compounds, organomagnesium compounds, organoaluminum compounds, and examples of the metal compounds include alkali metal hydrides and alkaline earth metal hydrides. To be Specific compounds include n-butyl lithium, sec-butyl lithium, phenyl sodium, sodium naphthalene, potassium naphthalene, dibutyl magnesium, diethyl magnesium, triethyl aluminum, triisobutyl aluminum, diethyl aluminum chloride, ethyl aluminum dichloride, ethyl aluminum sesquichloride. , Diethylaluminum hydride, methylaluminoxane,
Sodium aluminum hydride and the like,
You may use these in combination. The mixing ratio of these compounds and the Ti compound varies depending on the combination of the respective compounds, but the molar ratio to the Ti compound is 0.01 to
The range is 10. In order to obtain a high hydrogenation rate, it is necessary to carry out the hydrogenation reaction at a mixing ratio with good hydrogenation activity.

It is effective to carry out the reduction reaction of the Ti compound in the presence of a polymer having an aliphatic double bond in order to keep the hydrogenation catalyst highly active. Examples of preferred polymers having an aliphatic double bond include 1,3-butadiene and isoprene polymers, which have a number average molecular weight of 500 or more and 10,
A liquid polymer of 000 or less is preferable from the viewpoint of handling. Furthermore, by adding alcohol or the like, the hydrogenation catalyst can be maintained at a high activity, and the preferred alcohol has 1 to 1 carbon atoms.
12 alcohols, such as methanol, ethanol and heptanol.

Although a continuous hydrogenation reaction using other metal-based catalysts is also possible, the reaction conditions are such that a heterogeneous catalyst or polymer is continuously fed into a high-pressure reaction tank whose pressure exceeds 1 MPa. This is very disadvantageous for commercial production because the equipment becomes very large. The solvent used for the hydrogenation reaction may be the same as the solvent used for the above-mentioned polymerization reaction, but the solvent having an aliphatic double bond may be hydrogenated to become a saturated bond solvent.

These hydrogenation reactions are exothermic reactions, and the hydrogenation temperature is 40 to 150 ° C., preferably 60 to 1 by a suitable method.
It is desirable to control the temperature to 20 ° C. If the temperature exceeds 150 ° C., the activity of the catalyst decreases, which is not preferable, and if the temperature is lower than 40 ° C., the reaction rate becomes remarkably slow and the productivity becomes poor. The pressure of hydrogen used may exceed 1 MPa, but a sufficiently high hydrogenation rate can be obtained at a pressure of 0.1 to 1 MPa. By increasing the average residence time of the polymer in the hydrogenation reaction tank, the average hydrogenation rate of the hydrogenated polymer obtained can be increased. The residence time is determined from the average hydrogenation rate and productivity, but the preferable average residence time is 10 to 1
00 minutes.

The hydrogenated polymer can be stably obtained by keeping it in the pipe for transferring from the hydrogenation reaction tank to the degassing tank for 3 minutes or more, and particularly 90% or more in the hydrogenation reaction tank. With the hydrogenated polymer having a hydrogenation rate, a hydrogenated polymer having a higher hydrogenation rate can be obtained during the transfer in the pipe. It is presumed that this is because a new unhydrogenated polymer is not mixed in the pipe and the hydrogenation reaction between the unreacted hydrogen gas remaining in the pipe and the polymer is efficiently performed. If the residence time of the hydrogenated polymer in the pipe for transfer is shorter than 3 minutes, a sufficient increase in the hydrogenation rate cannot be obtained, but a long residence time is not required and even if the residence time is 20 minutes or more. The hydrogenation rate does not improve further. The decompression valve for degassing may be located at any position in the pipe for transferring from the hydrogenation reaction tank to the degassing tank, but preferably it is installed near the degassing tank so that a high hydrogenation rate can be easily obtained. Installing a static mixer in the pipe or providing a stirring / mixing tank is also effective for achieving a high hydrogenation rate.

The hydrogenated polymer solution is subjected to treatment such as removal of the polymerization catalyst residue or hydrogenation catalyst by a known method or conversion into a stable compound, if necessary, and further a stabilizer or the like. After the addition, the solvent can be removed by a known method to recover the polymer. For these recovery methods, a method of directly removing the solvent from the polymer solution, a method of removing the solvent by steam stripping and then drying, a polymer solution is put into a suitable poor solvent that does not dissolve the polymer to make a solid, There is a method of collecting.

The stabilizers that can be added include hindered phenol-based stabilizers, phosphorus-based stabilizers, sulfur-based stabilizers, amine-based stabilizers, and the like.
These can be used alone or in combination.
When an extruder is used to recover the polymer, these stabilizers can also be added using the extruder. In addition to the usual additives in the obtained hydrogenated polymer, for example, light stabilizers, ultraviolet absorbers, softeners, plasticizers, inorganic fillers, colorants, lubricants, flame retardants, antistatic agents, foaming agents. Alternatively, other resins or elastomers can be blended and used. The hydrogenated polymer of the present invention has excellent weather resistance and is particularly useful as a raw material polymer for a resin composition or an elastomer composition.

The hydrogenated polymer of the present invention may be modified and used. Examples of the modification method include a method in which a compound that reacts with the active end of the polymer is bonded, and a method in which a compound having a functional group is directly grafted onto the hydrogenated polymer chain. Especially α, including maleic anhydride and glycidyl methacrylate
Modified hydrogenated polymers obtained by radically reacting β-unsaturated dicarboxylic acids, α, β-unsaturated monocarboxylic acids and their derivatives with hydrogenated polymers are useful as compatibilizers for various resins. is there.

[0030]

[Examples] The present invention will be specifically described below with reference to Examples, but the present invention is not limited thereto. <Measurement of Hydrogenation Rate> The hydrogenation rate was measured using proton NMR at 280 MHz.

<Ozone Decomposition> Ozone decomposition is performed by Y. Tanaka, H.
Sato, Y.Nakafutami, Y.Kashiwazaki, Macromolecules,
Based on the method described in 16 (12) , 1925 (1983), 100
It was carried out by dissolving milligram of polymer in 50 milliliter of chloroform and introducing oxygen gas containing ozone 1.5% at -30 ° C. at a flow rate of 150 milliliter / minute. The end was 1 minute after the potassium iodide solution turned yellow.

<Polymerization Example> Cyclohexane 115 dried and purified in a 200-liter autoclave purged with nitrogen.
Liter, 400 g of tetrahydrofuran, and 2.1 kg of styrene were charged, the temperature was raised to 70 ° C., and then n-
Polymerization was performed by adding a cyclohexane solution containing 6.4 g of butyl lithium. Subsequently, 9.8 kilograms of 1,3-butadiene and 2.1 kilograms of styrene were sequentially added, and after the polymerization was completed, 2.5 grams of methanol was added to give a number average molecular weight of about 180,000 and 1 part of the polybutadiene portion. , 2-vinyl bond content of 35% SB
A complete block copolymer solution of S structure was obtained. This block copolymer is referred to as polymer (A).

<Preparation of hydrogenation catalyst 1> A reaction vessel purged with nitrogen was charged with 2 liters of dried and purified cyclohexane, and the molecular weight was about 40 mmol of bis (η ⁵ -cyclopentadienyl) titanium di (p-tolyl). 1,000 1,2-polybutadiene (1,2-vinyl bond content about 85
%) After dissolving 150 grams, n-butyllithium 6
Cyclohexane solution containing 0 mmol was added at 25 ° C.
The reaction was carried out for 5 minutes, and 40 mmol of n-butanol was immediately added and stirred and stored at room temperature. This solution is referred to as a hydrogenation catalyst solution (a).

<Preparation of hydrogenation catalyst 2> 1 liter of dried and purified toluene was charged into a reaction vessel purged with nitrogen, 20 mmol of bis (η ⁵ -cyclopentadienyl) titanium dichloride and 1,2 having a molecular weight of about 1,000 were prepared. 80 g of polybutadiene (1,57-vinyl bond content about 57%) were dissolved. A cyclohexane solution containing 120 mmol of triethylaluminum was added to the solution, reacted at 25 ° C for 2 minutes, and immediately stored in a refrigerator at 0 ° C. This solution is referred to as a hydrogenation catalyst solution (b).

(Comparative Example 1) 20 liters of a cyclohexane solution of the polymer (A) obtained in the polymerization example was charged into a 30 liter autoclave purged with nitrogen, and the atmosphere was replaced with hydrogen to raise the hydrogen pressure to 0.7 MPa (gauge pressure). The temperature was raised to 70 ° C. Next, 200 ml of the hydrogenation catalyst solution (a) was added with stirring, and hydrogen was continuously supplied for 2 hours so that the hydrogen pressure became 0.7 MPa (gauge pressure). The hydrogenated polymer was directly desolvated to give about 2 kilograms. The average hydrogenation rate of the obtained polymer is 9
It was 8.3%. This polymer is a hydrogenated polymer (1)
And In addition, the GPC curve (A) of the hydrogenated polymer (1) and the GPC curve (B) of a decomposition product obtained by ozone decomposition of the hydrogenated polymer (1) are shown in FIG. 1, and L2 / L1 was 0.

Example 1 A polymer (A) obtained in the above-mentioned polymerization example was placed in a 15-liter autoclave purged with nitrogen.
Was charged with 10 liters of the cyclohexane solution, and the hydrogen pressure was raised to 0.7 MPa (gauge pressure), and the temperature was raised to 70 ° C. Next, 100 ml of the hydrogenation catalyst solution (a) was added with stirring, and hydrogen was continuously supplied for 1 hour so that the hydrogen pressure became 0.7 MPa (gauge pressure). When a small amount of this polymer was sampled, the average hydrogenation rate was 97.8% and L2 / L1 was 0. Next, the solution of polymer (A) was continuously added from the bottom of the autoclave at a flow rate of 250 ml / min and the hydrogenation catalyst solution (a) at a flow rate of 2.5 ml / min. A pipe was installed in the degassing tank, the hydrogenated polymer was continuously extracted, and continuous hydrogenation was performed. The reaction temperature was controlled so as to be maintained at 70 ° C., and the hydrogen pressure was controlled at 0.7 MPa (gauge pressure). The average residence time of the polymer in the pipe from the autoclave to the degassing tank was 15 minutes, the temperature of the polymer solution immediately before the degassing tank was 40 ° C, and the average residence time at a temperature of 60 ° C or lower was 10 minutes. . When the polymer was sampled 4 hours after starting the continuous hydrogenation, the average hydrogenation rate at the hydrogenation reaction tank outlet and the degassing tank inlet was 9
It was 6.1% and 98.2%, and L2 / L1 was 0.04 and 0.04, respectively. A GPC curve (A) of these hydrogenated polymers and a GPC curve (B) of the decomposed products of the hydrogenated polymers subjected to ozone decomposition are shown in FIGS. 2 and 3. Directly desolvating from the polymer solution sampled in the degassing tank after the 4th hour, 2 kg of hydrogenated polymer (2) was obtained.

(Example 2) According to the above-mentioned polymerization example except that the monomer addition amount was 2.4 kg of styrene, 9.2 kg of butadiene, and 2.4 kg of styrene, the number average molecular weight of the SBS structure was about 178000. A complete block copolymer was obtained. Using this polymer and the hydrogenation catalyst (b), a hydrogenation reaction was carried out according to Example 1.
The hydrogenation catalyst (b) is kept cold at 0 ° C just before the addition,
The catalyst was used within 12 hours after preparation. The average hydrogenation rate in batch hydrogenation with a hydrogenation time of 1 hour is 96.4%, L2
/ L1 was 0. When the polymer was sampled 4 hours after switching to continuous hydrogenation in the same manner as in Example 1, the average hydrogenation rates at the hydrogenation reaction tank outlet and the degassing tank inlet were 95.3% and 96.9%. And L2 / L1 was 0.03 and 0.03, respectively.

(Example 3) Polymerization was carried out according to the above-mentioned polymerization example, and the number average molecular weight equivalent to that of the polymer (A) was 181,00.
0 polymer was obtained. Using this polymer, the degassing tank piping was extended from the hydrogenation reaction tank of Example 1, sampling nozzles were installed at five locations, and batch hydrogenation was switched to continuous hydrogenation by the method of Example 1. A hydrogenation reaction was carried out using the hydrogenation catalyst (a). Hydrogenated polymer sampled from each sampling nozzle 4 hours after switching to continuous hydrogenation
The average hydrogenation rate, L2 / L1, and the average residence time from the hydrogenation reaction tank to each sampling nozzle were as shown in Table 1 below.

[0039]

[Table 1]

Comparative Example 2 Polymerization was carried out according to the above-mentioned polymerization example, and the number average molecular weight equivalent to that of the polymer (A) was 183,00.
0 polymer was obtained. 20 liters of this polymer solution was charged into the autoclave used in Comparative Example 1, and hydrogenated using a hydrogenation catalyst composed of cobalt naphthenate and triethylaluminum at a hydrogen pressure of 6.9 MPa and a hydrogenation temperature of 60 ° C. for 5 hours. The autoclave was returned to normal pressure, the catalyst was added again, the hydrogen pressure was increased to 6.9 MPa, the temperature was kept at 50 ° C. for 3 hours, and the hydrogenation reaction was repeated. After removing the hydrogenation catalyst with hydrogen peroxide and tartaric acid, the solvent was directly removed to obtain 2 kg of hydrogenated polymer (3). The average hydrogenation rate of this hydrogenated polymer (3) was 99.7%, and L2 / L1 was 0.
It was 01. FIG. 4 shows the GPC curve (A) of the hydrogenated polymer (3) and the GPC curve (B) of the decomposed product of the hydrogenated polymer (3) subjected to ozone decomposition.

(Example 4, Comparative Examples 3 and 4) Hydrogenated polymers (2), (1), obtained in Example 1 and Comparative Examples 1 and 2,
The weather resistance of the elastomer composition using (3) was evaluated. The compounding composition used was 90 parts of a softening agent (PW380 manufactured by Idemitsu Kosan Co., Ltd.), 35 parts of polypropylene (M1600 manufactured by Asahi Kasei Kogyo Co., Ltd.), and a stabilizer (Irganox-made by Ciba-Geigy Co., Ltd.) per 100 parts of each hydrogenated polymer. 1076) 1 part, light stabilizer (American ACC, Ciasorb UV3346L
D) 0.3 parts and calcium stearate 0.5 parts, and this composition was added to a twin-screw extruder (PCM-3, manufactured by Ikegai Steel Co., Ltd.)
0) was used and pelletized at a resin temperature of 235 ° C. 2mmt press-molded at 200 ℃ using the obtained pellets
A JIS No. 3 dumbbell was prepared from the sheet, and a change in tensile strength was measured by performing a fade meter test under conditions of 83 ° C. and no rain. The results are shown in Table 2.

[0042]

[Table 2]

[0043]

EFFECT OF THE INVENTION The hydrogenated polymer of the present invention having L2 / L1 of 0.02 or more has excellent weather resistance and is particularly useful as a raw material polymer for a resin composition or an elastomer composition.
Further, the modified hydrogenated polymer obtained by reacting the hydrogenated polymer of the present invention with a compound having a functional group is useful as a compatibilizing agent for various resins.

[Brief description of drawings]

FIG. 1 is a normalized GPC curve of a hydrogenated polymer (1) obtained in Comparative Example 1 and a decomposition product obtained by ozonolysis thereof.

FIG. 2 is a normalized GPC curve of a hydrogenated polymer having an average hydrogenation rate of 96.1% sampled at the outlet of the hydrogenation reaction tank in Example 1 and a decomposition product obtained by ozone decomposition of the hydrogenation polymer.

FIG. 3 is a normalized GPC curve of a hydrogenated polymer (2) obtained in Example 1 and a decomposition product obtained by ozonolysis of the hydrogenated polymer (2).

FIG. 4 is a normalized GPC curve of a hydrogenated polymer (3) obtained in Comparative Example 2 and a decomposition product obtained by ozonolysis thereof.

[Explanation of symbols]

A Normalized GPC curve of hydrogenated polymer (1) (A) B Normalized GPC curve of ozone decomposed hydrogenated polymer (1) (B) Vertical line L1 perpendicular line drawn from the apex of the peak of L 1 Length of L L2 Distance on the perpendicular L between the intersection of the CPC curve B and the perpendicular L and the baseline

─────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-5-222115 (JP, A) JP-A-6-313013 (JP, A) JP-A-2-51503 (JP, A) JP-A-7- 258362 (JP, A) JP-A-4-248815 (JP, A) JP-A-61-47706 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08F 8/00-8 / 50

Claims (5)

(57) [Claims] 1. From a conjugated diene polymer obtained by anionic polymerization, a copolymer of a conjugated diene and a vinyl aromatic hydrocarbon having a vinyl aromatic hydrocarbon content (S) of 70% by weight or less, and a mixture thereof. Polymer solution and hydrogen gas
And hydrogenation catalyst are continuously added to a hydrogenation reaction tank equipped with a stirrer.
By the continuous hydrogenation method, the reaction product is continuously added
A hydrogenated polymer obtained by hydrogenating an aliphatic double bond mainly based on a conjugated diene in the obtained polymer, wherein the maximum molecular weight of the peak in the normalized GPC curve (A) of the hydrogenated polymer is obtained. The length of the perpendicular line L drawn from the apex of the peak of the component to the base line is L1, and the normalized G of the decomposition product obtained by ozone decomposition of the hydrogenated polymer
When the PC curve (B) is superposed on the GPC curve (A) at the same elution time, the GPC curve (B) shows a perpendicular line L.
The distance on the perpendicular L between the intersection and the baseline is L
When it is set to 2, L2 / L1 is 0.02 or more and less than 1.0. Average hydrogenation rate (H) (%) of double bond based on conjugated diene
Is a value satisfying the following general formula (1), and the styrene-equivalent weight average molecular weight (Mw) obtained by GPC is 30,
000 to 1,000,000 hydrogenated polymers. [Formula 1] 2. Conjugated diene polymerization obtained by anionic polymerization
Body or vinyl aromatic hydrocarbon content (S) is 70
Copolymerization of Concentrated Conjugated Diene with Vinyl Aromatic Hydrocarbon
And a polymer solution composed of a mixture thereof and hydrogen gas.
And hydrogenation catalyst are continuously added to a hydrogenation reaction tank equipped with a stirrer.
In addition to the continuous hydrogenation method, the reaction product is continuously extracted.
3 minutes into the pipe that transfers the hydrogenation reaction tank to the degassing tank.
Obtained by a continuous hydrogenation method characterized by holding for more than
The hydrogenated polymer according to claim 1. 3. Conjugated diene polymerization obtained by anionic polymerization
Body or vinyl 70% aromatic hydrocarbon content (S)
Copolymerization of Concentrated Conjugated Diene with Vinyl Aromatic Hydrocarbon
And a polymer solution composed of a mixture thereof and hydrogen gas.
Obtained by reducing a compound represented by the following general formula (2)
The hydrogenation catalyst to be continuously added to a hydrogenation reaction tank equipped with a stirrer.
In addition to the continuous hydrogenation method, the reaction product is continuously extracted.
3 minutes into the pipe that transfers the hydrogenation reaction tank to the degassing tank.
Obtained by a continuous hydrogenation method characterized by holding for more than
The hydrogenated polymer according to claim 1. [Chemical 1] Cp ₂  MRR '(2) [In the formula, Cp may be substituted with an alkyl group.
Lopentadienyl group, M is titanium, zirconium
R and R'are halogens.
Selected from alkyl, aryl having 1 to 12 carbon atoms, and aryl
And R and R'may be the same or different.
Yes. ] 4. Conjugated diene polymerization obtained by anionic polymerization
Body or vinyl aromatic hydrocarbon content (S) is 70
Copolymerization of Concentrated Conjugated Diene with Vinyl Aromatic Hydrocarbon
And a polymer solution composed of a mixture thereof and hydrogen gas.
And hydrogenation catalyst are continuously added to a hydrogenation reaction tank equipped with a stirrer.
In addition to the continuous hydrogenation method, the reaction product is continuously extracted.
3 minutes into the pipe that transfers the hydrogenation reaction tank to the degassing tank.
Characterized by being obtained by a continuous hydrogenation method in which it is held for at least a period of time
The method for producing a hydrogenated polymer according to claim 1. 5. The hydrogenation catalyst is represented by the following general formula (2).
Characterized by being a hydrogenation catalyst obtained by reducing a compound
The method for producing a hydrogenated polymer according to claim 4. [Chemical 1] Cp ₂  MRR '(2) [In the formula, Cp may be substituted with an alkyl group.
Lopentadienyl group, M is titanium, zirconium
R and R'are halogens.
Selected from alkyl, aryl having 1 to 12 carbon atoms, and aryl
And R and R'may be the same or different.
Yes. ]